Although molecular dinitrogen (N2) is widely used as a carrier or inert gas for many catalytic reactions, it is rarely considered as a catalytic promoter. Here, we report that N2 could be used to reduce the activation energy for catalytic hydrodeoxygenation over ruthenium-based catalysts. Specifically, we report a 4.3-fold activity increase in the catalytic hydrodeoxygenation of p-cresol to toluene over a titanium oxide supported ruthenium catalyst (Ru/TiO2) by simply introducing 6 bar N2 under batch conditions at 160 °C and 1 bar hydrogen. Detailed investigations indicate that N2 can be adsorbed and activated on the metallic ruthenium surface to form hydrogenated nitrogen species, which offer protic hydrogen to lower the activation energy of direct carbonaromatic–oxygen bond scission and the hydrogenation of hydroxy groups. Thus, by employing different ruthenium catalysts, including Ru/TiO2, Ru/Al2O3, Ru/ZrO2 and Ru/C, we demonstrate that N2 promotion of hydrodeoxygenation can be regarded as a general strategy.
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The data that support the plots within this paper and other findings of this study are available from the corresponding author uon reasonable request.
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H.D. thanks SCG Chemicals, SCG Packaging (Thailand) and the National Natural Science Foundation of China (Grant No. 21978147). Y.Z. thanks the National Natural Science Foundation of China (Grant No. 21878008) and the Fundamental Research Funds for the Central Universities (BUCTRC201807). X.M. thanks the National Natural Science Foundation of China (21902182) and the Fundamental Research Funds for the Central Universities (2019QH01). J.D. acknowledges support from the Youth Innovation Promotion Association CAS. X.Z. thanks the National Natural Science Foundation of China (Grant No. 11875258). J.-C.B. thanks SCG Chemicals (Thailand) for funding. We also thank the Hefei Light Source and Shanghai Light Source for use of instruments and the Diamond Light Source for access and support in the use of the electron Physical Science Imaging Centre (EM16969, 17397), which contributed to the results presented here. J.L. thanks the National Natural Science Foundation of China (Grand Nos. 21433005, 91645203 and 21590792). The calculations were performed using the supercomputers at Tsinghua National Laboratory for Information Science and Technology. We also thank Y. Li for providing characterization resources and S. Ji for performing ICP analysis. We thank C. Chen for performing TPR measurement, W.-C. Lin for helping with the fixed-bed reactions and Y. Yang for assisting with the FTIR measurements.
The authors declare no competing interests.
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Duan, H., Liu, JC., Xu, M. et al. Molecular nitrogen promotes catalytic hydrodeoxygenation. Nat Catal 2, 1078–1087 (2019). https://doi.org/10.1038/s41929-019-0368-6
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